ChemInform Abstract: HYDROXYARYLIERUNG VON DIVINYL MIT ARYLDIAZONIUMSULFATEN, ‐NITRATEN UND ‐TETRAFLUOROBORATEN

Abstract

Die Aryldiazoniumsulfate (I) reagieren mit Divinyl (II) in Gegenwart von CuSO und FeSO4 in wäßrigem Aceton bei ‐5°C bis 0°C und pH 5‐7 (NaHCO3‐Zusatz) zu Gemischen der Arylbutenole (III) und (IV).

Intermolecular Olefin Functionalisation Involving Aryl Radicals Generated from Arenediazonium Salts

“…Copper-mediated carbohydroxylation and carboacetoxylation of 1,3-butadiene (8) and isoprene (35). [64] Scheme 13. Carbothionylation reactions employing potassium thiocyanate in the presence of copper(II) tetrafluoroborate.…”

“…[64] The capability of copper(II) ions to transfer ligands to allyl radicals via the formation of a copperA C H T U N G T R E N N U N G (III)-allyl intermediate has been proposed as mechanism for comparable reactions (Scheme 5). [38,65] While acetate ligands can be directly transferred to give the isomeric esters 36, the alcohols 33 are believed to evolve from the hydrolysis of previously formed sulfate esters.…”

“…[38,65] While acetate ligands can be directly transferred to give the isomeric esters 36, the alcohols 33 are believed to evolve from the hydrolysis of previously formed sulfate esters. [64] An overview over reactions of aromatic diazonium salts with unsaturated compounds in the presence of oxygen and sulfur nucleophiles has been given by Grishchuk. [66] Scheme 9.…”

Modern Developments in Aryl Radical Chemistry

“…The first carbooxygenation reactions in which aryl radicals were involved have been reported for 1,3-dienes [104,105]. With photochemically generated aryl radicals and in presence of the aminooxyl radical TEMPO as radical scavenger, carbooxygenations could at first only be extended to activated alkenes [106].…”

Recent Advances in Meerwein Arylation Chemistry

“…Carbooxygenation of alkenes is feasible under transition-metal catalysis 49 as well as through a number of radical reactions. Early copper(II)-mediated Meerwein arylations of this type were limited to conjugated dienes, 50,51 thereby suggesting that a copper(III)-allyl complex 22 is necessary to transfer oxygen-containing ligands, such as acetate, to the alkene unit. A broad variety of alkenes were functionalized in iron(II)-mediated carbooxygenations with arenediazonium salts as the radical source and TEMPO (tetramethylpiperidin-1-oxyl radical) as the oxygen-centered radical scavenger.…”